CN116589639A - Thermoplastic methyl methacrylate resin system and method for in-situ injection pultrusion of fiber reinforced material - Google Patents

Thermoplastic methyl methacrylate resin system and method for in-situ injection pultrusion of fiber reinforced material Download PDF

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Publication number
CN116589639A
CN116589639A CN202310413572.1A CN202310413572A CN116589639A CN 116589639 A CN116589639 A CN 116589639A CN 202310413572 A CN202310413572 A CN 202310413572A CN 116589639 A CN116589639 A CN 116589639A
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pmma
mma
resin system
pultrusion
methyl methacrylate
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咸贵军
田凌宇
张朴轩
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
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    • B29C70/28—Shaping operations therefor
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    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
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    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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Abstract

The invention discloses a thermoplastic methyl methacrylate resin system and a method for in-situ injection pultrusion of fiber reinforced materials thereof, belonging to the technical field of resin matrix composite material preparation. Firstly, PMMA is dissolved in MMA, and filler is added to obtain a PMMA-MMA system with certain viscosity; then adding an initiator, a dispersing agent and a release agent, and uniformly stirring to obtain a PMMA-MMA resin system for in-situ injection pultrusion; finally, the fiber is impregnated by using a glue injection device, the temperature is raised and cured, and the in-situ injection and pultrusion molding is completed, so that the fiber reinforced thermoplastic composite material is obtained. The PMMA-MMA resin system provided by the invention can realize efficient fiber impregnation, and realize in-situ polymerization of MMA monomers in the system at a certain temperature and time to prepare the fiber reinforced material. Solves the problems of uncontrolled prepolymerization, low production efficiency and low-temperature storage and transportation in the preparation of the existing thermoplastic methacrylate resin system.

Description

Thermoplastic methyl methacrylate resin system and method for in-situ injection pultrusion of fiber reinforced material
Technical Field
The invention relates to a thermoplastic methyl methacrylate resin system and a method for in-situ injection pultrusion of fiber reinforced materials thereof, belonging to the technical field of resin matrix composite material preparation.
Background
The fiber reinforced resin matrix composite has the advantages of light weight, high strength, corrosion resistance, fatigue resistance and the like, and is widely applied to the fields of aerospace, light weight automobiles, building materials, wind power blades and the like. Compared with the fiber reinforced thermosetting resin matrix composite, the fiber reinforced thermoplastic resin matrix composite has the advantages of high production efficiency, small pollution, high raw material utilization rate, higher toughness and impact strength, recyclability, welding performance and long service life, but thermoplastic resins such as polyether ether ketone, polypropylene, polyamide and polyvinyl chloride are solid at room temperature and poor in fluidity in a molten state, so that fiber impregnation is difficult, and popularization and application of the fiber reinforced thermoplastic resin matrix composite are restricted.
The thermoplastic methacrylate resin has low viscosity, and the in-situ polymerization can be used for preparing the fiber reinforced thermoplastic composite material with high impregnation degree, high fiber content and high performance, so that the problems of large equipment investment and high production cost of the thermoplastic composite material are solved. However, when the methacrylate resin for in-situ polymerization molding is prepared, the high heat release amount leads to the high temperature in a mold cavity to cause the polymerization to be out of control, the production efficiency is low, and the initiator and the accelerator contained in the system need to be stored and transported at low temperature, so that the fiber reinforced methacrylate resin matrix composite material cannot be popularized and applied on a large scale. Chinese patent CN102181115A proposes a polymethacrylate product and a preparation method thereof, but in the practical process, after PMMA and MMA are uniformly mixed, an initiator is added, PMMA is dissolved by reaction heat, the dissolution effect is poor, the viscosity of the system is up to 10000 Pa.S to 200 ten thousand Pa.S, the system can not be applied to in-situ injection and pultrusion of fiber reinforced thermoplastic composite materials, MMA is exploded by the reaction heat, and the initiator still needs to be stored and transported at low temperature in a PMMA-MMA system.
Disclosure of Invention
The invention aims at the defects in the prior art and provides a thermoplastic methyl methacrylate resin system and a method for in-situ injection pultrusion of a fiber reinforced material by the same.
The technical scheme of the invention is as follows:
it is an object of the present invention to provide a thermoplastic methyl methacrylate resin system comprising a PMMA-MMA composite resin, an initiator, a mold release agent and a dispersant; wherein the viscosity of the PMMA-MMA composite resin is 100-1000 mPa.S, and the PMMA-MMA composite resin consists of PMMA, MMA and filler.
Further defined, the PMMA-MMA composite resin comprises, by mass, 40-80 parts of PMMA, 20-60 parts of MMA and 0.5-30 parts of filler.
Further limiting, mixing PMMA, MMA and filler, and dissolving at 60-220 ℃ to obtain the PMMA-MMA composite resin.
Further defined, the initiator is 0.5-3 parts by mass, the release agent is 0.5-3 parts by mass, and the dispersant is 0.5-2 parts by mass.
Further defined, the initiator is one or a mixture of more of tert-butyl perbenzoate, nitrogen-nitrogen dimethyl-p-toluidine, dibenzoyl peroxide and azodiisobutyronitrile.
Further defined, the filler is one or more of aluminum hydroxide, precipitated silica, light calcium carbonate, heavy calcium carbonate, clay, organoclay and mica powder.
Further defined, the dispersant is a modified polyurethane solution.
Still further defined, the dispersant is BYK-W974.
Further defined, the release agent is an organic fatty acid, a lipid and amine mixed solution.
The second object of the invention is to provide a preparation method of the thermoplastic methyl methacrylate resin system, which comprises the steps of dissolving PMMA in MMA at 60-220 ℃, adding filler to obtain PMMA-MMA composite resin with viscosity of 100-1000 mPa.S, cooling to 20-30 ℃, adding initiator, release agent and dispersing agent, and stirring uniformly to obtain PMMA-MMA resin system for in-situ injection pultrusion.
The invention further provides a method for in-situ impregnation injection pultrusion of the thermoplastic methyl methacrylate resin system to form the fiber reinforced material.
Further defined, the elevated temperature curing conditions are: constant temperature of 80-180 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, PMMA is used as a main raw material, and through melting in MMA and adjusting the mass ratio of PMMA, filler and MMA, the specific regulation and control of the viscosity of the PMMA-MMA composite resin are realized, the heat release amount and the solidification shrinkage rate in the subsequent product molding process are reduced, and the problem of uncontrolled MMA prepolymerization in the preparation of methacrylate resin for in-situ injection pultrusion is solved.
(2) The invention can separate and preserve PMMA-MMA resin system and other components (initiator, filler and dispersing agent) for in-situ injection pultrusion of fiber reinforced thermoplastic composite material, and solves the problems of low-temperature storage and transportation of the resin system.
(3) The invention adopts the organic fatty acid as the release agent, has high compatibility with PMMA-MMA resin system for in-situ injection and pultrusion, can improve the fluidity of a matrix, improves the linear speed, has wetting and coupling effects on fillers, fibers and the like, improves the mechanical properties of products, and migrates to the surfaces of the products to form chemical reaction films in the curing process, keeps the isolation between the products and a die, and ensures the smoothness of the surfaces of the products.
(4) The thermoplastic methyl methacrylate resin system provided by the invention can be applied to the preparation of fiber reinforced materials in-situ impregnation injection pultrusion, and the product has good mechanical properties and durability, has extremely broad application prospects in the fields of aerospace, automobile industry, construction, energy sources, energy storage and the like, and can obviously improve economic benefits.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The parts in the examples below are all in parts by mass and all materials in the examples are commercially available. The dispersant is BYK-W974, and the release agent is NODA-1968.
Example 1:
in the embodiment, the resin of the continuous preparation fiber reinforced thermoplastic methyl methacrylate resin matrix composite is formed by in-situ impregnation injection pultrusion. The method comprises the following specific steps:
first, the technology before molding:
threading, namely leading out glass fiber tows from the fiber creel, and passing through the yarn guide plate, the pultrusion die and the traction device; stretching the fiber, clamping and stretching the fiber tows by using a traction device, and controlling the tension of the tows within a limit value range; the pultrusion die was preheated and heated to 120 ℃.
In the second step, a thermoplastic methacrylate resin is prepared.
Weighing 40 parts of PMMA, 30 parts of filler nano aluminum hydroxide and 60 parts of MMA, completely dissolving PMMA particles in the MMA at 200 ℃, and then adding the filler nano aluminum hydroxide to obtain a PMMA-MMA system with the viscosity of 800 mPa.S; and cooling the PMMA-MMA system to 25 ℃, adding 1 part of dibenzoyl peroxide, 0.5 part of dispersing agent and 2 parts of release agent, and fully and uniformly mixing to obtain the PMMA-MMA resin system.
Thirdly, in-situ impregnation injection pultrusion:
and transferring the PMMA-MMA resin system into a glue injection machine, and connecting the injection gun with a glue injection port of the pultrusion die.
(1) Injecting glue for impregnation, pumping thermoplastic methacrylate resin into a mould from a glue injection machine, and completing fiber impregnation in a pultrusion mould;
(2) And (3) carrying out pultrusion, starting a traction device, drawing the fiber tows to pass through a pultrusion die, and carrying out polymerization reaction (the temperature in the die is 120 ℃) on the thermoplastic methacrylate resin in the pultrusion die to form an integral composite material part with the fibers, so as to finish the molding.
The fiber reinforced thermoplastic methyl methacrylate composite material has smooth surface and no any broken filaments, the degree of fiber impregnation of the product is 97 percent according to the standard GBT3365-2008, the fiber volume fraction is 62 percent, and the tensile strength of the product is 1350MPa and the bending strength of the product is 1300MPa according to the standard GBT 13096-2008.
Comparative example 1:
the specific preparation process of the comparative example is as follows:
first, the technology before molding:
threading, namely leading out glass fiber tows from the fiber creel, and passing through the yarn guide plate, the pultrusion die and the traction device; stretching the fiber, clamping and stretching the fiber tows by using a traction device, and controlling the tension of the tows within a limit value range; the pultrusion die was preheated and heated to 120 ℃.
In the second step, a thermoplastic methacrylate resin is prepared.
Weighing 40 parts of PMMA and 60 parts of MMA, and uniformly mixing to obtain a PMMA-MMA system; 1 part of dibenzoyl peroxide, 30 parts of filler nano aluminum hydroxide, 0.5 part of dispersing agent and 2 parts of release agent are added into the PMMA-MMA system, PMMA particles have poor solubility and burst phenomenon, and the PMMA-MMA system cannot be applied to in-situ impregnation injection pultrusion mode to form fiber reinforced thermoplastic methyl methacrylate resin matrix composite materials.
Comparative example 2:
the specific preparation process of the comparative example is as follows:
first, the technology before molding:
threading, namely leading out glass fiber tows from the fiber creel, and passing through the yarn guide plate, the pultrusion die and the traction device; stretching the fiber, clamping and stretching the fiber tows by using a traction device, and controlling the tension of the tows within a limit value range; the pultrusion die was preheated and heated to 120 ℃.
In the second step, a thermoplastic methacrylate resin is prepared.
Weighing 40 parts of PMMA, 30 parts of filler nano aluminum hydroxide and 60 parts of MMA, completely dissolving PMMA particles in the MMA at 200 ℃, and then adding the filler nano aluminum hydroxide to obtain a PMMA-MMA system with the viscosity of 800 mPa.S; and cooling the PMMA-MMA system to 25 ℃, adding 1 part of dibenzoyl peroxide and 0.5 part of dispersing agent, and fully and uniformly mixing to obtain the PMMA-MMA resin system.
Thirdly, in-situ impregnation injection pultrusion:
and transferring the PMMA-MMA resin system into a glue injection machine, and connecting the injection gun with a glue injection port of the pultrusion die.
(1) Injecting glue for impregnation, pumping thermoplastic methacrylate resin into a mould from a glue injection machine, and completing fiber impregnation in a pultrusion mould;
(2) And (3) carrying out pultrusion, starting a traction device, drawing the fiber tows to pass through a pultrusion die, and carrying out polymerization reaction (the temperature in the die is 120 ℃) on the thermoplastic methacrylate resin in the pultrusion die to form an integral composite material part with the fibers, so as to finish the molding.
The surface of the fiber reinforced thermoplastic methyl methacrylate composite material is provided with ravines, and the phenomena of broken filaments and fibers occur, the degree of fiber impregnation of the product is 95 percent according to the standard GBT3365-2008, the fiber volume fraction is 61 percent, and the tensile strength of the product is 1150MPa and the bending strength is 1050MPa according to the standard GBT 13096-2008.
Comparative example 3:
the specific preparation process of the comparative example is as follows:
first, the technology before molding:
threading, namely leading out glass fiber tows from the fiber creel, and passing through the yarn guide plate, the pultrusion die and the traction device; stretching the fiber, clamping and stretching the fiber tows by using a traction device, and controlling the tension of the tows within a limit value range; the pultrusion die was preheated and heated to 120 ℃.
In the second step, a thermoplastic methacrylate resin is prepared.
Weighing 40 parts of PMMA and 60 parts of MMA, and completely dissolving PMMA particles in MMA at 200 ℃ to obtain a PMMA-MMA system; and cooling the PMMA-MMA system to 25 ℃, adding 1 part of dibenzoyl peroxide, 30 parts of nano aluminum hydroxide serving as a filler and 0.5 part of a dispersing agent, and fully and uniformly mixing to obtain the PMMA-MMA resin system.
Thirdly, in-situ impregnation injection pultrusion:
and transferring the PMMA-MMA resin system into a glue injection machine, and connecting the injection gun with a glue injection port of the pultrusion die.
(1) Injecting glue for impregnation, pumping thermoplastic methacrylate resin into a mould from a glue injection machine, and completing fiber impregnation in a pultrusion mould;
(2) And (3) carrying out pultrusion, starting a traction device, drawing the fiber tows to pass through a pultrusion die, and carrying out polymerization reaction (the temperature in the die is 120 ℃) on the thermoplastic methacrylate resin in the pultrusion die to form an integral composite material part with the fibers, so as to finish the molding.
Voids appear on the surface of the fiber-reinforced thermoplastic methyl methacrylate composite material, the degree of fiber impregnation of the product is measured to be 91% according to the standard GBT3365-2008, the fiber volume fraction is measured to be 62%, and the tensile strength of the product is measured to be 1130MPa and the bending strength is measured to be 1080MPa according to the standard GBT 13096-2008.
The inventive embodiments disclosed above are merely intended to help illustrate the inventive embodiments. The examples are not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention.

Claims (10)

1. A thermoplastic methyl methacrylate resin system for in-situ injection pultrusion is characterized by comprising PMMA-MMA composite resin, an initiator, a dispersing agent and a release agent; wherein the viscosity of the PMMA-MMA composite resin is 100-1000 mPa.S, and the PMMA-MMA composite resin consists of PMMA, MMA and filler.
2. Thermoplastic methyl methacrylate resin system for in-situ injection pultrusion according to claim 1, characterized in that the PMMA-MMA composite resin comprises 40-80 parts by mass of PMMA, 20-60 parts by mass of MMA and 0.5-30 parts by mass of filler.
3. The thermoplastic methyl methacrylate resin system for in-situ injection pultrusion according to claim 1, characterized in that PMMA and MMA are mixed and dissolved at 60-220 ℃ and filler is added to obtain PMMA-MMA composite resin.
4. The thermoplastic methyl methacrylate resin system for in-situ injection pultrusion according to claim 1, characterized in that the initiator is 0.5-3 parts by mass, the dispersant is 0.5-2 parts by mass, and the release agent is 0.5-3 parts by mass.
5. The thermoplastic methyl methacrylate resin system for in-situ injection pultrusion according to claim 1, characterized in that the initiator is one or a mixture of several of tert-butyl perbenzoate, nitrogen-nitrogen dimethyl para-toluidine, dibenzoyl peroxide, azodiisobutyronitrile.
6. The thermoplastic methyl methacrylate resin system for in-situ injection pultrusion according to claim 1, characterized in that the filler is one or a mixture of several of aluminum hydroxide, precipitated silica, light calcium carbonate, heavy calcium carbonate, clay, organoclay, mica powder.
7. The thermoplastic methyl methacrylate resin system for in-situ injection pultrusion of claim 1, characterized in that the dispersing agent is a modified polyurethane solution.
8. The thermoplastic methyl methacrylate resin system for in-situ injection pultrusion of claim 7, wherein the mold release agent is an organic fatty acid.
9. A method for preparing a thermoplastic methyl methacrylate resin system according to claim 1, which is characterized in that PMMA and filler are dissolved in MMA at 60-220 ℃ to obtain PMMA-MMA composite resin with the viscosity of 100-1000 mPa.s, the PMMA-MMA composite resin is cooled to 20-30 ℃, and an initiator, a release agent and a dispersing agent are added and stirred uniformly to obtain the PMMA-MMA resin system for in-situ injection pultrusion.
10. A method for in-situ dip injection pultrusion of a thermoplastic methyl methacrylate resin system according to claim 1, characterized in that a PMMA-MMA resin system is placed in a glue injection machine, and then pumped into a pultrusion die to finish fiber dipping, and the fibers are pulled through the pultrusion die and cured at a temperature rise to obtain the fiber reinforced thermoplastic composite material.
CN202310413572.1A 2023-04-18 2023-04-18 Thermoplastic methyl methacrylate resin system and method for in-situ injection pultrusion of fiber reinforced material Pending CN116589639A (en)

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